Process Solutions Containing Surfactants

ABSTRACT

Process solutions comprising one or more surfactants are used to reduce the number of defects in the manufacture of semiconductor devices. In certain embodiments, the process solution may reduce post-development defects such as pattern collapse or line width roughness when employed as a rinse solution either during or after the development of the patterned photoresist layer. Also disclosed is a method for reducing the number of defects such as pattern collapse and/or line width roughness on a plurality of photoresist coated substrates employing the process solution of the present invention.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a divisional of U.S. patent application Ser. No.10/804,513, filed on Mar. 19, 2004, which is a continuation-in-part ofU.S. patent application Ser. Nos. 10/218,087, filed 12 Aug. 2002,10/339,709, filed 9 Jan. 2003, and 10/616,662 filed 10 Jul. 2003, thedisclosures of which are incorporated herein by reference in theirentirety.

BACKGROUND OF THE INVENTION

The present invention relates generally to methods for the manufactureof semiconductor devices. More specifically, the present inventionrelates to a method for reducing defects, particularly pattern collapseand photoresist line roughness, in semiconductor devices incurred duringthe manufacturing process without sacrificing throughput.

Defects are a major limiting factor for production yield and devicefunction, particularly when the device sizes are reduced and wafer sizesare enlarged to 300 mm. The term “defects”, as used herein, relates todefects that may reduce the yield, or cause the loss, of thesemiconductor device such as the collapse of the photoresist pattern onthe substrate surface; roughness in the photoresist lines such as “linewidth roughness” or “line edge roughness”, particulates introduced ontothe substrate resulting from processing such as lithography, etching,stripping, and chemical mechanical planarization (CMP) residues;particulates either indigenous to or resulting from manufacturingprocesses; pattern imperfections such as closed or partially open orblocked contacts or vias; line width variations; and defects resultingfrom poor adhesion of the resist to the substrate surface.

The drive to reduce defects—thereby improving yield—presents newchallenges to the manufacturing steps within the production of thesemiconductor device, namely, the lithography, etching, stripping, andchemical-mechanical planarization (CMP) processes. The lithographyprocess generally involves coating a substrate with a positive ornegative photoresist, exposing the substrate to a radiation source toprovide an image, and developing the substrate to form a patternedphotoresist layer on the substrate. This patterned layer acts as a maskfor subsequent substrate patterning processes such as etching, doping,and/or coating with metals, other semiconductor materials, or insulatingmaterials. The etching process generally involves removing the surfaceof the substrate that is not protected by the patterned photoresistusing a chemical or plasma etchant thereby exposing the underlyingsurface for further processing. The stripping process generally involvesremoving the cross-linked, photoresist pattern from the substrate viawet stripping or oxygen plasma ashing. The CMP process generallyinvolves polishing the surface of the substrate to maintain flatnessduring processing. All of the aforementioned processes typically employa rinse step to remove any particulate material that is generated from,or is a by-product of, these processes.

Pattern collapse is becoming an emerging problem in the production ofsemiconductor devices due to the higher aspect ratios in the newgeneration of devices. The thickness and aspect ratio of the patternedphotoresist layer are important parameters for subsequent etch stepsafter lithography. At the 130 nm node, the aspect ratio for aphotoresist layer having a 500 nm thickness may reach the value of 4.This value may be the point where the capillary force of the developerand/or rinse solution may lead to the collapse of the patternedphotoresist layer. Besides capillary forces, the pattern collapseproblem may be further influenced by other factors such as themechanical strength of the resist, application of other coatings, i.e.,anti-reflective coatings (ARC), and the nozzle type, position, andcentrifugal forces during spin-on application of the photoresist layer.

A main contributor for pattern collapse is the capillary force of waterduring the post-development drying stage, see Tanaka, T., et al.,“Mechanism of Resist Pattern Collapsed During Developer Process”, Jpn.J. Appl. Phys., Vol. 32, 1993, pp. 6059-64. Reducing or eliminating thesurface tension of the rinse liquid after pattern development may beused to reduce the capillary force that is exerted on the patternedphotoresist layer. Two common approaches, to reduce or eliminate thesurface tension of the rinse liquid, may be to freeze-dry the patternedphotoresist features or employ supercritical fluids to dry the patternedphotoresist layer after development. Both of these approaches mayrequire extra manufacturing steps and special equipment that are notcommonly used in semiconductor device fabrication.

A more common approach to reduce the surface tension may be to add asurfactant to the rinse liquid. The ability to reduce the surfacetension of water at the air and liquid interface is of great importancein a variety of applications because decreased surface tension generallyrelates to increased wetting of water on the substrate surface. Surfacetension reduction in water-based systems is generally achieved throughthe addition of surfactants. Equilibrium surface tension performance isimportant when the system is at rest, though the ability to reducesurface tension under dynamic conditions is of great importance inapplications where high surface creation rates are used, i.e., spincoating, rolling, spray coating, and the like. Dynamic surface tensionprovides a measure of the ability of the solution to lower surfacetension and provide wetting under high speed application conditions.Further, in certain applications such as during spray application, it isadvantageous that the surfactant reduces the surface tension of theformulation in a manner that minimizes the problem of bubble generationand foaming. Foaming and bubble generation may lead to defects.Consequently, considerable efforts have been made in the semiconductorindustry towards solving the foaming problem.

Japanese patent JP 95142349A describes adding a fluorine-basedsurfactant such as ammonium perfluoroalkylsulfonate or perfluoroalkylethoxylate to the developer solution or rinse liquid.

U.S. Pat. No. 6,152,148 describes adding a surfactant such as afluorosurfactant and a tetra alkyl quaternary ammonium hydroxidecompound to an aqueous solution used to clean semiconductor wafershaving a poly(arylene ether) dielectric film coating after CMP.

The article, Domke, W. D et al., “Pattern Collapse in High Aspect RatioDUV- and 193 nm Resists”, Proc. SPIE-Int. Soc. Opt. Eng. 3999, 313-321,2000 (“Domke”), describes adding surfactants to the developer solutionto reduce the possibility of pattern collapse of acrylic andcycloolefin-maleic anhydride resists. The “surfactant” added todeveloper solution was the solvent, isopropyl alcohol. According toDomke, the addition of the “surfactant” in the developer solution didnot have a consistent effect on pattern collapse.

PCT application WO 02/23598 describes adding the surfactant ammoniumlauryl sulfate into the deionized (DI) water rinse and developer andapplying them to a patterned photoresist to minimize or eliminatepost-development defects.

Japanese Patent Application JP 96008163A describes adding hot water, anorganic solvent, and a surfactant to a post-development rinse to preventpattern collapse. No specific surfactants were mentioned.

PCT application 87/03387 describes protecting photoresist images againstdistortion or degradation by heat generated during etching and otherprocesses by applying a thermally stabilizing, protective film to thesubstrate prior to the post-development bake of the image. Materialsused for the film includes fluorocarbon surfactants, film formingpolymers, chromium sulfate, trichloroacetic acid, chromotropic acid, andsalts thereof.

The article, Cheung, C. et al., “A Study of a Single Closed Contact for0.18 micron Photolithography Process” Proc. SPIE-Int. Soc. Opt. Eng.3998, 738-741, 2000 (“Cheung”), discloses the use of surfactants such asoctyl and nonyl phenol ethoxylates such as TRITON® X-114, X-102, X-45,and X-15, in the rinse solution to eliminate the photoresist residue andsingle closed contact defects. According to Cheung, the use ofsurfactant in the rinse solution did not provide much success.

U.S. Pat. No. 5,977,041 describes a post-stripping, aqueous rinsesolution that includes water, a water soluble organic acid, and a watersoluble surface-active agent. The surface-active agents includeoligo(ethylene oxide) compounds having at least one acetylenic alcoholgroup.

WO 00/03306 describes a stripper composition that comprises an admixtureof a solvent and a surfactant wherein the amount of solvent ranges fromabout 50 to about 99.9 weight percent of the total composition and theamount of surfactant ranges from about 0.1 to about 30 weight percent ofthe total composition.

U.S. Patent Application No. 2002/0115022 describes a developer and arinse solution that each contains an anionic surfactant such as ammoniumperfluoroalkyl sulfonate or ammonium perfluoroalkyl carboxylate. Thesesolutions are applied in a consecutive sequence to reduce patterncollapse.

The article “Collapse Behavior of Single Layer 193 and 157 nm Resists:Use of Surfactants in the Rinse to Realize the Sub 130 nm Nodes:, Hienet al., Advances in Resist Tech. And Processing XIX, Proceedings ofSPIE, Vol. 4690 (2002), pp. 254-261 (“Hien”), applying a rinse solutionof 0.10% of a fluorosurfactant and water to a substrate afterdevelopment to reduce pattern collapse. According to Hein, some of thefluorosurfactants used worsened the collapse behavior.

Yet another emerging problem in the production of semiconductor devicesis photoresist roughness such as in one edge of a single photoresistline which is referred to herein as line edge roughness (LER), or bothedges of photoresist line which is referred to herein as line widthroughness (LWR). Line width roughness is typically measured by thevariation of line width from its required critical dimension (“CD”). The2003 International Technology Roadmap for Semiconductors requires thatthe LWR be within 8% of the CD. For example, the LWR, as measured by the3σ variation of line width, would be within 3 nm for the 90 nmtechnology node and within 2.0 for the 65 nm node. A variety of factors,that may contribute to photoresist line roughness, include, for example,photoresist formulation (i.e., molecular weight, molecular weightdistribution, resist polymer structures, photo-acid generators) andprocess and tool-related factors (i.e., acid diffusion, developerpercolation, shot noise, mask roughness, and the quality of the latentimage profile). Previous attempts to reduce photoresist line roughnessdefects include modifying the photoresist formulation and adjusting thecontrast of the latent image.

Although surfactants have been commonly used as a post-development rinsesolution, these solutions may not be effective in reducing the surfacetension under dynamic conditions. Further, these solutions may have theundesirable side effect of foam generation. Because of these issues, therinse solution using typical surfactants used in the art may not beeffective in reducing all of the defects, particularly pattern collapsedefects, in the semiconductor device.

All references cited herein are incorporated herein by reference intheir entirety.

BRIEF SUMMARY OF THE INVENTION

The present invention satisfies some, if not all, of the needs of theart by providing a process solution and methods for using same.Specifically, in one aspect of the present invention, there is provideda method for reducing defects in the manufacture of semiconductordevices. The method comprises: providing a substrate comprising aphotoresist coating; exposing the substrate to a radiation source toform a pattern on the photoresist coating; applying a developer solutionto the substrate to form a patterned photoresist coating; optionallyrinsing the substrate with deionized water; and contacting the substratewith a process solution comprising a solvent and 10 ppm to about 10,000ppm of at least one surfactant having the formula (I), (II), (III),(IVa), (IVb), (V), (VI), (VII), (VIII), (IXa), (IXb), (IXc), (Xa), (Xb),(Xc), or (Xd):

wherein R, R₁, R₄, and R₁₂ are each independently a straight, abranched, or a cyclicalkyl group having from 2 to 250, or from 3 to 10carbon atoms; R₂ and R₃ are each independently a hydrogen atom or analkyl group having from 1 to 10 or from 1 to 5 carbon atoms; R₅ is astraight, a branched, or a cyclic alkyl group having from 1 to 10 carbonatoms; R₆ is a straight, a branched, or a cyclic alkyl group having from4 to 16 carbon atoms; R₇, R₈, and R₉ are each independently a straight,a branched, or a cyclic alkyl group having from 1 to 6 carbon atoms; R₁₀is independently H or a group represented by the following formula

R₁₁ is a straight, a branched, or a cyclic alkyl group having from 4 to22 carbon atoms; W is a hydrogen atom or an alkynyl group; X and Y areeach independently a hydrogen atom or a hydroxyl group; Z is a halideatom, a hydroxyl group, an acetate group, or a carboxylate group; i, m,n, p, and q are each independently a number that ranges from 0 to 20; rand are each independently 2 or 3; t is a number that ranges from 0 to2; j is a number between 1 to 5; and x is a number that ranges from 1 to6.

In yet a further aspect of the present invention, there is provided amethod for avoiding a collapse of a developed pattern on the surface ofa plurality of substrates and reducing photoresist line roughnesscomprising: providing a first substrate comprising a photoresist patterndeveloped upon the surface; preparing a process solution comprising from10 ppm to about 10,000 of at least one surfactant having the formulas(I), (i), (III), (IVa), (IVb), (V), (VI), (VII), (VIII), (IXa), (IXb),(IXc), (Xa), (Xb), (Xc), or (Xd) described herein; contacting the firstsubstrate with the process solution; determining a surface tension and acontact angle of the process solution on the first substrate;multiplying the surface tension by the cosine of the contact angle toprovide the adhesion tension value of the process solution; providingthe plurality of substrates wherein each substrate within the pluralitycomprises a photoresist pattern developed upon the surface; andcontacting the plurality of substrates with the process solution if theadhesion tension value of the process solution is 30 or below.

In yet a further aspect of the present invention, there is provided aprocess rinse solution to reduce pattern collapse defects on the surfaceof a substrate that has been patterned and developed comprising at leastone carrier medium selected from the group consisting of an aqueoussolvent or a non-aqueous solvent and at least one surfactant selectedfrom the group of surfactants having the formula (I), (II), (III),(IVa), (IVb), (V), (VI), (VII), (VIII), (IXa), (IXb), (IXc), (Xa), (Xb),(Xc), or (Xd) described herein.

These and other aspects of the invention will become apparent from thefollowing detailed description.

BRIEF DESCRIPTION OF SEVERAL VIEWS OF THE DRAWINGS

FIG. 1 a provides a cross-sectional scanning electron micrograph (SEM)image of a 193 nm photoresist coated substrate having 80 nm dense lines,a 1:1 pitch, and a 3.75 aspect ratio that has been treated with adeionized water rinse.

FIG. 1 b provides a cross-sectional SEM image of a 193 nm photoresistcoated substrate having 80 nm dense lines, a 1:1 pitch, and a 3.75aspect ratio that has been treated with a process solution of thepresent invention.

FIGS. 2 a through 2 c provide cross-sectional SEM images of a 193 nmphotoresist coated substrate after treatment with deionized water; aprocess solution of the present invention containing a Formula Vsurfactant and Formula III surfactant; and a process solution of thepresent invention containing a Formula VIII surfactant, respectively.

DETAILED DESCRIPTION OF THE INVENTION

The present invention is directed to process solutions that are used toreduce the number of defects incurred during the manufacturing of thesemiconductor device and methods of using same. It is believed thattreatment of a substrate with the process solution having one or moresurfactants—present in minor amounts—may provide at least one offollowing benefits: reduce post-development defects by improving thewetting of the solution on the surface of the patterned photoresistlayer; reduce the capillary forces exerted on the patterned linesthereby contributing to pattern collapse defects; improve thephotoresist line roughness regardless of the origin of the lineroughness. Further, the process solution works more effectively indynamic rinse situations with relatively minor foam generation comparedto other surfactants presently used in the art.

The process solution of the present invention can be used in a varietyof processes related to the manufacture of a semiconductor device suchas for example, lithography process solutions, i.e., rinse, resist, edgebead remover, and anti-reflective coating (ARC) solutions; post-etchingprocess solutions, i.e., sidewall film, stripper, post-strip/ash rinsesolutions; wafer cleaning process solutions, i.e., additives to RCA orother standard cleaning solutions, super-critical CO₂ cleaningsolutions; and process solutions for critical cleaning or precisioncleaning for aerospace applications. In certain preferred embodiments,the process solution of the present invention may be employed as alithography rinse solution in addition to, or in place of, a deionizedwater rinse. The surfactant within the process solution may allow forthe reduction of equilibrium and dynamic surface tension whileminimizing foaming.

The process solution of the present invention may have as a carrierphase or medium an aqueous-based solvent and/or non-aqueous-basedsolvent. The term “aqueous” as used herein, describes a solvent orliquid dispersing medium, which comprises at least 80 weight percent,preferably 90 weight percent, and more preferably at least 95 weightpercent water. The preferred aqueous-based solvent is deionized water.In embodiments wherein the process solution is aqueous-based, it isdesirable that at least one formula I through X surfactant demonstratesa dynamic surface tension of less than 45 dynes/cm at a concentration ofless than or equal to 5 weight percent in water at 23° C. and 1bubble/second according to the maximum-bubble-pressure method ofmeasuring surface tension described in Langmuir 1986, 2, 428-432, whichis incorporated herein by reference in its entirety.

In embodiments where a non-aqueous solvent is used in addition to or inplace of an aqueous solvent such as water, the non-aqueous solventselected will not react with the at least one surfactant containedtherein, other additives within the process solution, or the substrateitself. Suitable solvents include, but are not limited to, hydrocarbons(e.g. pentane or hexane); halocarbons (e.g. Freon 113); ethers (e.g.ethylether (Et₂O), tetrahydrofuran (“THF”), ethylene glycol monomethylether, or 2-methoxyethyl ether (diglyme)); nitriles (e.g. CH₃CN); oraromatic compounds (e.g. benzotrifluoride). Still further exemplarysolvents include lactates, pyruvates, and diols. These solvents include,but are not limited to, acetone, 1,4-dioxane, 1,3-dioxolane, ethylacetate, cyclohexanone, acetone, 1-methyl-2-pyrodidianone (NMP), andmethyl ethyl ketone. Other solvents, include dimethylformamide,dimethylacetamide, N-methyl pyrrolidone, ethylene carbonate, propylenecarbonate, glycerol and derivatives, naphthalene and substitutedversions, acetic acid anhydride, propionic acid and propionic acidanhydride, dimethyl sulfone, benzophenone, diphenyl sulfone, phenol,m-cresol, dimethyl sulfoxide, diphenyl ether, terphenyl, and the like.Still further solvents include propylene glycol propyl ether (PGPE),methanol, ethanol, 3-heptanol, 2-methyl-1-pentanol, 5-methyl-2-hexanol,3-hexanol, 2-heptagon, 2-hexanol, 2,3-dimethyl-3-pentanol, propyleneglycol methyl ether acetate (PGMEA), ethylene glycol, isopropyl alcohol(PI), n-butyl ether, propylene glycol n-butyl ether (PGBE),1-butoxy-2-propanol, 2-methyl-3-pentanol, 2-methoxyethyl acetate,2-butoxyethanol, 2-ethoxyethyl acetoacetate, 1-pentanol, and propyleneglycol methyl ether. The non-aqueous solvents enumerated above may beused alone or in combination with two or more solvents.

In certain embodiments, the process solution may contain at least onenon-aqueous solvent that is miscible in an aqueous solvent or iswater-miscible. In these embodiments, the amount of non-aqueous solventwithin the process solution may range from about 1 to about 50% byweight with the balance of the solvent within the process solutioncomprising an aqueous solvent. Examples of water-miscible non-aqueoussolvents include methanol, ethanol, isopropyl alcohol, and THF.

The present solution comprises from 10 to 10,000 ppm of at least onesurfactant represented by structural formulas I through X. Typicalsurfactants exhibit an amphiphilic nature, meaning that they can be bothhydrophilic and hydrophobic at the same time. Amphiphilic surfactantspossess a hydrophilic head group or groups, which have a strong affinityfor water and a long hydrophobic tail, which is organophilic and repelswater. The at least one formula I through X surfactant used in thepresent invention may be ionic (i.e., anionic, cationic) or nonionic.

In certain embodiments of the present invention, the process solutionmay contain one or more nonionic surfactants that are acetylenic diolderivatives. The surfactants of the present invention may be representedby the following formula I or formula II:

wherein R₁ and R₄ are each independently a straight or a branched alkylchain having from 3 to 10 carbon atoms; R₂ and R₃ are each independentlya hydrogen atom or an alkyl chain having from 1 to 5 carbon atoms; andi, m, n, p, and q are each independently a number that ranges from 0 to20. The surfactants are commercially available from Air Products andChemicals, Inc. of Allentown, Pa., the assignee of the presentinvention, under the trade names SURFYNOL® and DYNOL®. In certainpreferred embodiments, the acetylenic diol portion of the molecule offormulas I or II is 2,4,5,9-tetramethyl-5-decyne-4,7-diol or2,5,8,11-tetramethyl-6-dodecyne-5,8-diol. The acetylenic diol derivedsurfactants may be prepared in a number of ways including the methodsdescribed, for example, in U.S. Pat. No. 6,313,182 and EP 1115035A1which are assigned to the assignee of the present invention andincorporated herein by reference in their entirety.

In formula I and II, the alkylene oxide moieties represented by (OC₂H₄)are the (n+m) polymerized ethylene oxide (EO) molar units and themoieties represented by (OC₃H₆) are the (p+q) polymerized propyleneoxide (PO) molar units. The value of (n+m) may range from 0 to 30,preferably from 1.3 to 15, and more preferably from 1.3 to 10. The valueof (p+q) may range from 0 to 30, preferably from 1 to 10, and morepreferably from 1 to 2.

In certain preferred embodiments of the present invention, the processsolution contains from 10 to 10,000 ppm of at least one surfactantrepresented by the following formulas (III) through (X):

In each of the above formulas, R, R₁, R₄, and R₁₂ are each independentlya straight, a branched, or a cyclic alkyl group from 2 to 25 or from 3to 10 carbon atoms; R₂ and R₃ are each independently a hydrogen atom ora straight, a branched, or a cyclic alkyl group having from 1 to 10, orfrom 1 to 5 carbon atoms; R₅ is a straight, a branched, or a cyclicalkyl group with 1 to 10 carbon atoms; R₆ is a straight or branchedalkyl group with 4 to 16 carbon atoms; R₇, R₈ and R₉ are eachindependently a straight, a branched, or a cyclic alkyl group havingfrom 1 to 6 carbon atoms; R₁₀ is independently H or a group representedby the formula

R₁₁ is a straight, a branched, or a cyclic alkyl group having from 4 to22 carbon atoms; W is a hydrogen atom or an alkynyl group; X and Y areeither a hydrogen atom or a hydroxyl group; Z⁻ is either a halide atom,a hydroxyl group, an acetate group, or a carboxylate group; i, m, n, p,q are each independently a number ranging from 0 to 20; r and s are eachindependently 2 or 3; t is a number ranging from 0 to 2; j is a numberranging from 1 to 5; and x is a number ranging from 1 to 6. Examples ofFormula III surfactants include, but are not limited to,3,5-dimethyl-1-hexyn-3-ol and 2,6-dimethyl-4-heptanol. An example of aFormula IVa surfactant includes, but is not limited to,N,N′-bis(1,3-dimethylbutyl)ethylene diamine. An example of a Formula Vsurfactant includes, but is not limited to, diisopentyl tartrate. Anexample of a Formula VI surfactant includes, but is not limited to,dodecyltrimethylammonium chloride. An example of a Formula VIIsurfactant includes, but is not limited to,2,4,7,9-tetramethyl-4,7-decane diol. An example of a Formula VIIIsurfactant includes, but is not limited to, an adduct ofdiethylenetriamine and n-butyl glycidyl ether. Formula IXa, IXb, or IXcsurfactants are primary, secondary, or tertiary alkyl amines. An exampleof a Formula IXa surfactant includes, but is not limited to, octylamine.Formula Xa, Xb, Xc, or Xd surfactants are alkyl amine ethoxylates.

The process solution may optionally contain a dispersant. The amount ofdispersant that is added to the process solution ranges from about 10 toabout 10,000 ppm, preferably about 10 to about 5,000 ppm, and morepreferably from about 10 to about 1,000 ppm. The term dispersant, asused herein, describes compounds that enhance the dispersion ofparticles such as dust, processing residue, hydrocarbons, metal oxides,pigment or other contaminants within the process solution. Dispersantssuitable for the present invention preferably have a number averagemolecular weight that ranges from about 10 to about 10,000.

The dispersant may be an ionic or a nonionic compound. The ionic ornonionic compound may further comprise a copolymer, an oligomer, or asurfactant, alone or in combination. The term copolymer, as used herein,relates to a polymer compound consisting of more than one polymericcompound such as block, star, or grafted copolymers. Examples of anonionic copolymer dispersant include polymeric compounds such as thetri-block EO-PO-EO co-polymers PLURONIC® L121, L123, L31, L81, L101 andP123 (BASF, Inc.). The term oligomer, as used herein, relates to apolymer compound consisting of only a few monomer units. Examples ofionic oligomer dispersants include SMA® 1440 and 2625 oligomers (ElfAlfochem).

Alternatively, the dispersant may comprise a surfactant. If thedispersant comprises a surfactant, the surfactant may be ionic (i.e.,anionic, cationic) or nonionic. Further examples of surfactants includesilicone surfactants, poly(alkylene oxide) surfactants, andfluorochemical surfactants. Suitable non-ionic surfactants for use inthe process solution include, but are not limited to, octyl and nonylphenol ethoxylates such as TRITON® X-114, X-102, X-45, X-15 and alcoholethoxylates such as BRIJ® 56 (C₁₆H₃₃(OCH₂CH₂)₁₀OH) (ICI), BRIJ® 58(C₁₆H₃₃(OCH₂CH₂)₂₀OH) (ICI). Still further exemplary surfactants includealcohol (primary and secondary) ethoxylates, amine ethoxylates,glucosides, glucamides, polyethylene glycols, poly(ethyleneglycol-co-propylene glycol), or other surfactants provided in thereference McCutcheon's Emulsifiers and Detergents, North AmericanEdition for the Year 2000 published by Manufacturers ConfectionersPublishing Co. of Glen Rock, N.J.

Various other additives may be optionally added to the process solutiondepending upon the application. These additives may include, but are notlimited to, stabilizers, dissolving aids, colorants, wetting agents,antifoamers, buffering agents, and other additional surfactants.Generally, unless otherwise stated, the amount of each of theseadditives would be about 0.0001 to 1 percent by weight, more preferably0.0001 to 0.1 percent by weight, based upon the total weight of theprocess solution. In embodiments where one or more additionalsurfactants are added to the process solution, the surfactant may be anyof the surfactants disclosed herein or provided in the referenceMcCutcheon's Emulsifiers and Detergents.

In certain embodiments, the process solution of the present inventionmay be used as a non-aqueous photoresist. In this connection, theprocess solution preferably comprises from 60 to 90, preferably from 70to 90 weight percent non-aqueous solvent; from 5 to 40 weight percent,preferably from 10 to 20 weight percent resist polymer; from 0.5 toabout 2 weight percent of a photoactive compound; 10 to 10,000 ppm of atleast one formula I through X surfactant; and less than 1 weight percentof other additives such as polymerization inhibitors, dyes,plasticizers, viscosity control agents, and the like. The viscosity ofthe photoresist can be adjusted by varying the polymer to solvent ratio,thus allowing resists to be formulated for coating a variety of filmthickness. Examples of suitable non-aqueous solvents within thephotoresist process solution include any of the solvents containedherein. Non-limiting examples of a resist polymer include novolac resinor polyvinyl phenol copolymer. Non-limiting examples of a photoactivecompounds include diazonaphthoquinone or photo acid generators (PAG).

The process solution of the present invention may also be used as anon-aqueous edge bead remover. Edge bead removers may be applied priorto baking the patterned photoresist layer to cross-link the polymertherein or prior to lithography. In this embodiment, the processsolution preferably comprises from 99 to 100 weight percent non-aqueoussolvent; 10 to 10,000 ppm of at least one formula I through Xsurfactant; and less than 1 weight percent of other additives. Examplesof suitable non-aqueous solvents within the edge bead remover processsolution include any of the solvents contained herein. In certainpreferred embodiments, the solvent may be PGMEA, ethyl lactate, oranisole.

The process solution of the present invention may also be used as ananti-reflective coating for the top or bottom surface of the substrate.In this embodiment, the process solution preferably comprises from 60 to99 weight percent non-aqueous solvent; from 1 to 40 weight percent,preferably 1 to 20 weight percent of a polymer; from 10 to 10,000 ppm ofat least one formula I through X surfactant; and less than 1 weightpercent of other additives such as crosslinker(s), surfactant(s), dyecompounds, and the like. In general, the solids content of the processsolution may vary from about 0.5 to about 40, preferably 0.5 to about20, and more preferably 2 to 10 weight percent of the total weight ofthe process solution. Examples of suitable non-aqueous solvents withinthe ARC process solution include any of the solvents contained herein.In certain preferred embodiments, the solvent may be PGMEA or ethyllactate. Examples of suitable polymers within the ARC process solutioninclude, but are not limited to, acrylate polymers or phenyl-containingpolymers such as those disclosed in U.S. Pat. No. 6,410,209 andspin-on-glass materials such as the methylsiloxane,methylsilsesquioxane, and silicate polymers such as those disclosed inU.S. Pat. Nos. 6,268,457 and 6,365,765.

The process solution of the present invention may be used in wafercleaning methods, such as RCA-type cleaning, performed after thedevelopment step. In this embodiment, the substrate may be treated withthe process solution after the stripping, CMP, ash cleaning, and/oretching steps have been completed. In one embodiment of the presentinvention, the process solution comprises a base such as an amine and/orammonium hydroxide, alkylammonium hydroxide; an oxidizing agent such asH₂O₂; optionally a chelating agent; from 10 to 10,000 ppm of at leastone formula I through X surfactant; in an aqueous solvent or water. Somenon-limiting examples of chelating agents are the following organicacids and its isomers and salts: (ethylenedinitrilo)tetraacetic acid(EDTA), butylenediaminetetraacetic acid,cyclohexane-1,2-diaminetetraacetic acid (CyDTA),diethylenetriaminepentaacetic acid (DETPA),ethylenediaminetetrapropionic acid, ethylenediaminetetrapropionic acid,(hydroxyethyl)ethylenediaminetriacetic acid (HEDTA),N,N,N′,N′-ethylenediaminetetra(methylenephosphonic) acid (EDTMP), citricacid, tartaric acid, phtalic acid, gluconic acid, saccharic acid,cathechol, gallic acid, pyrogallol, propyl gallate, and cysteine. In analternative embodiment, the process solution comprises dilute HF; from10 to 10,000 ppm of at least one formula I through X surfactant; andwater. In a further embodiment, the process solution comprises an acidsuch as sulfuric acid or HCl and an oxidizing agent such as H₂O₂ whereinthe ratio of the acid to the oxidizing agent is 1:1; optionally achelating agent; from 10 to 10,000 ppm of at least one formula I throughX surfactant; and an aqueous solvent or water. In another embodiment,the process solution comprises an aqueous solvent such as electrolyticionized water and from 10 to 10,000 ppm of at least one formula Ithrough X surfactant. In yet another embodiment, the process solutioncomprises UV/ozone; from 10 to 10,000 ppm of at least one formula Ithrough X surfactant; and water. For wafer cleaning applications, theprocess solution may be used for either megasonic or regular cleaningsuch as spray application.

The process solution of the present invention may be prepared by mixingthe at least one formula I through X surfactant with an aqueous and/ornon-aqueous solvents and any additional additives. In certainembodiments, the mixing may be done at a temperature range of about 40to 60° C. to affect dissolution of the ingredients contained therein.The resulting process solution may optionally be filtered to remove anyundissolved particles that could potentially harm the substrate.

The process solution is preferably used to treat the surface of asubstrate during or after the development step. Suitable substratesinclude, but are not limited to, materials such as gallium arsenide(“GaAs”), silicon, tantalum, copper, ceramics, aluminum/copper alloys,polyimides, and compositions containing silicon such as crystallinesilicon, polysilicon, amorphous silicon, epitaxial silicon, silicondioxide (“SiO₂”), silicon nitride, doped silicon dioxide, and the like.Further exemplary substrates include silicon, aluminum, or polymericresins.

In certain preferred embodiments, the process solution is applied to asubstrate having a photoresist coating applied thereto. Thephotoresist-coated substrate is then exposed to radiation to provide apattern that is imposed upon the photoresist coating. Examples ofradiation sources that may be used include ultraviolet (uv) light,electron beam, x-ray, laser, or ion beams. In some embodiments, apre-bake or soft-bake step may be conducted prior to the exposure stepto remove any solvents contained therein. This pre-bake or soft bakestep may be conducted, for example, at a temperature ranging from 90° C.to 150° C. for a time of from 30 to 120 seconds on a hot plate.

Depending upon whether the photoresist coating is positive or negative,the radiation either increases or decreased its solubility in asubsequently applied, an alkaline developer solution such as a processsolution containing tetramethylammonium hydroxide (TMAH), potassiumhydroxide, sodium hydroxide, or other base. Further examples ofdeveloper solutions include those provided in U.S. Pat. Nos. 6,455,234;6,268,115; 6,238,849; 6,127,101; and 6,120,978. In a positivephotoresist coating, the areas masked from radiation remain afterdevelopment while the exposed areas are dissolved away. In a negativephotoresist coating, the opposite occurs. The process solution of thepresent invention may be suitable to treat substrates having eitherpositive or negative photoresist coatings. The patterned photoresistimage may be developed by a variety of different means, including by notlimited to quiescence, immersion, spray, or puddle development. In thequiescence method, for instance, a developer solution is applied to theexposed substrate surface and after a period of time sufficient todevelop the pattern, a rinse is then applied to the substrate surface.Development time and temperatures will vary depending upon the methodused.

After the patterned photoresist image is developed, the substrate isbaked to harden the polymer contained within the photoresist. The bakestep may be conducted, for example, at a temperature ranging from 70° C.to 150° C. for a time duration of from 30 to 120 seconds.

The process solution is preferably applied to the surface of thesubstrate as a prepared solution. In alternative embodiments, however,the process solution can be prepared within the rinse stream just priorto or during contact with the substrate surface. For example, a certainquantity of one or more formula I through IX surfactants can be injectedinto a continuous stream of water and/or non-aqueous solvent medium thatoptionally includes other additives thereby forming the processsolution. In some embodiments of the present invention, a portion of theat least one formula I through X surfactant may be added to thesubstrate after application of the process solution. In this case, theprocess solution may be formed in multiple steps during the processingof the substrate. In still other embodiments of the present invention,the at least one formula I through X surfactant can be also depositedupon or comprise the material of a high surface area device such as acartridge or filter (which may or may not include other additives). Astream of water and/or non-aqueous solvent then passes through thecartridge or filter thereby forming the process solution. In stillanother embodiment of the present invention, the process solution isprepared during the contacting step. In this connection, at least oneformula I through X surfactant is introduced via a dropper or othermeans to the surface of the substrate. Water and/or non-aqueous solventmedium is then introduced to the surface of the substrate and mixes withthe at least one formula I through X surfactant on the surface of thesubstrate thereby forming the process solution.

In an alternative embodiment of the invention, a concentratedcomposition comprising at least one formula I through X surfactant isprovided that may be diluted in water and/or non-aqueous solvents toprovide the process solution. A concentrated composition of theinvention, or “concentrate” allows one to dilute the concentrate to thedesired strength and pH. A concentrate also permits longer shelf lifeand easier shipping and storage of the product.

A variety of means can be employed in contacting the process solutionwith the substrate surface. The actual conditions of the contacting step(i.e., temperature, time, and the like) may vary over wide ranges andare generally dependent on a variety of factors such as, but not limitedto, the nature and amount of residue on the surface of the substrate andthe hydrophobicity or hydrophilicity of the substrate surface, etc. Thecontact step can be conducted in either a dynamic method such as, forexample, a streamline process for applying the process solution over thesurface of the substrate or in a static method such as, for example, apuddle rinse or immersing the substrate within a bath containing theprocess solution. The process solution may also be sprayed onto thesurface of the substrate in a dynamic method such as in a continuousprocess or sprayed onto the surface and allowed to remain there in astatic method. In certain preferred embodiments, the contacting step isconducted in a static method. The duration of the contacting step, ortime of contact of the process solution to the substrate surface, canvary from a fraction of a second to hundreds of seconds. Preferably, theduration can range from 1 to 200 seconds, preferably from 1 to 150seconds, and more preferably from 1 to 40 seconds. The temperature rangefor the contacting step can vary from 10 to 100° C. and more preferablyfrom 10 to 40° C.

Regardless of whether the contacting step is static or dynamic, it ispreferred that the process solution or concentrate be applied to astill-wet substrate surface. In one embodiment, for example, the processsolution is employed as a rinse solution after the development of thephotoresist layer. In this connection, the photoresist-coated substrateis developed via a developer solution. After developing, the processsolution is applied to the substrate surface as a rinse in addition to,or in place of, a deionized water rinse. While the substrate is stillwet with developer solution and/or deionized water, the process solutionmay be applied in a dynamic manner or in a static manner such as bypuddling it onto the surface of the substrate. During dispensing, thesubstrate is spun slowly at a speed, for example, of 100 revolutions perminute (“rpm”) to distribute the process solution over the substratesurface. For a dynamic process, the substrate is spun slowly while theprocess solution is dispensed continuously on the substrate. For astatic process such as the puddle process, the substrate is allowed torest for a brief period, for example, 15 seconds. After the rinse stepwith the process solution is complete, the rinsed wafer is then dried,for example, by spin drying at a higher rpm.

In yet a further embodiment of the present invention, there is provideda method for selecting the process solution comprising at least oneformula I through X surfactant that will minimize the number of patterncollapse defects for patterned, photoresist-coated substrates. In thisregard, the method comprises determining the surface tension and themeasuring the contact angle of a process solution containing from 10 to10,000 ppm of the at least one surfactant. The process solution is firstapplied to the surface of a sample photoresist-coated substrate. Thesurface tension, preferably dynamic surface tension, of the processsolution may be determined according to the maximum-bubble-pressuremethod as described herein. The contact angle of the process solution,which is the angle between the baseline of a droplet of process solutionon the surface of the substrate and the tangent at the droplet base, isthen measured. In certain preferred embodiments, a high-speed camera maybe used to capture the spreading of the droplet at a speed of 2 framesper second for a 2 minute interval and the contact angle can be measuredon the photographic image.

Once the surface tension and contact angle for the process solution isobtained, the surface tension is then multiplied by the cosine of thecontact angle measurement to provide a certain value referred to hereinas an “adhesion tension value”. Lower adhesion tension values for theprocess solution correlate to a greater reduction in pattern collapsedefects. Adhesion tension values of 30 or less indicate, preferably 25or less, or more preferably 20 or less indicate that the processsolution may be more effective in reducing the number of patterncollapse defects compared to deionized rinse solutions or processsolutions containing other surfactants described in the prior art. Ifthe adhesion tension value is acceptable (i.e., 30 or less), the processsolution may then be used for a production lot. The concentration of theformula I through X surfactant is determined by the smallest adhesiontension value calculated at different concentrations for eachsurfactant. In certain preferred embodiments, the process solutionreduced the number of pattern collapse defects by 25% or greater,preferably 50% or greater, and more preferably 75% or greater relativeto a deionized water rinse for patterned and developed photoresistcoated substrates having an aspect ratio of 3.0 or greater, and a pitchof 1:1.4 or greater, or a normalized aspect ratio of at least 0.0151/nm.

The invention will be illustrated in more detail with reference to thefollowing examples, but it should be understood that the presentinvention is not deemed to be limited thereto.

EXAMPLES Examples 1 Through 5 Dynamic Surface Tension (DST)

Five process solutions containing acetylenic diol surfactants derivedfrom 2,4,7,9-tetramethyl-5-decyne-4,7-diol (examples 1 through 3) or2,5,8,11-tetramethyl-6-dodecyne-5,8-diol (examples 4 and 5) wereprepared by adding 0.1 weight percent of the surfactant to deionizedwater under continuous stirring.

The dynamic surface tension (DST) data for each process solution wascollected via the maximum bubble pressure method described in Langmuir1986, 2, pp. 428-432. The data was collected at bubble rates that rangefrom 0.1 bubbles/second (b/s) to 20 b/s using the Kruss BP3 bubblepressure tensiometer manufactured by Kruss, Inc. of Charlotte, N.C. Themolar units of EO and PO for each example and dynamic surface tensiondata is provided in Table I.

The dynamic surface tension data provides information about theperformance of a surfactant at conditions from near-equilibrium (0.1b/s) to relatively high surface creation rates (20 b/s). Forapplications such as semiconductor or IC processing, high bubble ratesmay correspond to a faster substrate rotation speed or a dynamicdispense in a post-development rinse process. It is desirable that thedynamic surface tension by reduced below that of water at high bubblerates (i.e., 70-72 dyne/cm at 20 b/s) to provide, inter alia, betterwetting of the photoresist-coated substrate, reduction in the number ofdefects, and prevention of pattern collapse. As Table I illustrates, allof the process solutions exhibited dynamic surface tensions at highbubble rates below that of water. This indicates that the processsolutions of the present invention may be effective at reducing thesurface tension of water. TABLE I Dynamic Surface Tension DST DST DSTDST DST Ex- Moles Moles (dyne/ (dyne/ (dyne/ (dyne/ (dyne/ am- EO PO cm)cm) cm) cm) cm) ple (m + n) (p + q) 0.1 b/s 1 b/s 6 b/s 15 b/s 20 b/s 15 2 34.0 35.3 37.6 41.5 44.3 2 5 0 35.1 35.2 38.1 42.0 44.4 3 0 0 32.133.1 34.2 36.1 40.3 4 0 0 34.1 43.6 58.1 68.3 69.8 5 4 0 26.8 26.8 31.535.9 39.1

Examples 5 Through 7 Foaming Properties

Three process solutions containing acetylenic diol surfactants derivedfrom 2,4,7,9-tetramethyl-5-decyne-4,7-diol (examples 5 and 6) or2,5,8,11-tetramethyl-6-dodecyne-5,8-diol (example 7) were prepared byadding 0.1 weight percent of each surfactant to deionized water undercontinuous stirring.

Foaming is an undesirable side effect of surfactants in rinse solution.The foaming properties of examples 5 through 7 were examined using aprocedure based upon ASTM D 1173-53, the Ross-Miles test method, and theresults are provided in Table II. In this test, a 200 ml quantity ofeach process solution is added from an elevated foam pipette to a foamreceiver containing the 50 ml of the same solution at room temperature.The Ross-Miles method stimulates the action of pouring a liquid into acylindrical vessel containing the same liquid. The results are given inTable II. The foam height is measured at the completion of the addition(“Initial Foam Height”) and the time required for the foam to dissipateis recorded (“Time to 0 Foam”). In certain applications, foam may beundesirable because it may lead to defects due to the failure toadequately coat the surface of the substrate. As Table II indicates, thetime to reach zero foam is approximately one minute or less.

The process solution of Example 5 was also compared to process solutionscontaining 0.1 weight percent of a fluorosurfactant (perfluoroalkylethoxylate) and an ionic surfactant (sodium lauryl sulfate) using theRoss-Miles test. The results of this comparison are provided in TableIII. As Table III shows, solutions containing the fluorosurfactant andionic surfactant still exhibited significant foam at intervals of 5 or10 minutes. In semiconductor processing applications, the presence ofsignificant foam may be undesirable and may lead to an increase inprocessing defects. TABLE II Foaming Properties Moles EO Moles POInitial Foam Time to Zero Example (m + n) (p + q) Height (cm) Foam (sec)5 5 2 0.6 6 6 0 0 2.0 3 7 4 0 2.5 60

TABLE III Comparison of Foam Properties with Solutions containing otherSurfactants Initial Foam Foam Foam Foam Height Height Height RinseHeight at 6 sec at 5 min at 5 min Composition (cm) (cm) (cm) (cm)Example 5 0.6 0 0 0 Fluorosurfactant 14.5 14.5 N/A 13.5 (0.1 weight%)⁽¹⁾ Ionic surfactant 22.0 22.0 20.0 N/A (0.25 weight %)⁽²⁾⁽¹⁾Information obtained from DuPont ZONYL ® marketing literature.⁽²⁾Information obtained from Weil, J. K., et al., “Synthetic Detergentsfrom Animal Fats: the Sulfonation of Tallow Alcohols”, J. Am. Oil Chem.Soc. 31, p. 444-47 (1954).

Examples 8 Through 9 Contact Angle Data

The wetting properties of process solutions containing varying amountsof surfactants derived from 2,4,7,9-tetramethyl-5-decyne-4,7-diol(examples 8a and 8b) or 2,5,8,11-tetramethyl-6-dodecyne-5,8-diol(examples 9a and 9b) and DI water as a comparison (comparativeexample 1) was measured on the G10/DSA10 Kruss drop shape analyzerprovided by Kruss USA of Charlotte, N.C. using the Sessile drop method.In this method, the wetting properties of a localized region on thesurface of a photoresist-coated substrate are estimated by measuring thecontact angle between the baseline of a droplet of aqueous developersolution and the tangent at the droplet base. A high-speed cameracaptured the spreading of the droplet at a speed of 2 frames per secondfor 2 minutes and the contact angle was measured.

Process solutions of surfactant based on2,4,7,9-tetramethyl-5-decyne-4,7-diol and2,5,8,11-tetramethyl-6-dodecyne-5,8-diol were prepared in the followingmanner. A volumetric flask was charged with varying amounts of thesurfactant and DI water to reach a level of 100 ml at room temperature.The mixture was agitated until the surfactant was dissolved therein toform the process solution. The amounts of surfactant in the processsolutions of examples 8a, 8b, 9a and 9b are provided in Table IV.

Silicon wafers provided by Wafernet Inc. of San Jose, Calif. were coatedwith a AX 4318 photoresist coating provided by Sumitomo Chemical Co.,Ltd. of Osaka, Japan using a spin coating process at a spin speed of3200 rpm. The contact angle of the process solution on the photoresistsurface was measured. Table IV provides the value of the contact anglefor the process solutions and DI water (comparative example 1) atdifferent drop ages expressed in seconds.

In general, contact angles of about 200 or below may indicate completewetting of the substrate surface. As Table IV illustrates, the contactangles of TMAH developer on the photoresist-coated substrate that weretreated with the process solutions of the present invention are smallerthan the contact angle of the photoresist treated with DI water.Further, higher amounts of surfactant within the process solution maylead to more surfactant adsorption and improved wetting. TABLE IVContact Contact Contact Contact Amt Angle Angle Angle Angle ExampleSurfactant (0 sec) (5 sec) (10 sec) (30 sec) Comp. Ex. — 61.8 61.7 61.561.1 1 - DI water Ex. 8a 125 ppm 47.3 46.9 46.5 45.4 Ex. 8b 600 ppm 47.342.6 40.6 36.4 Ex. 9a 100 ppm 50.0 46.8 45.0 41.6 Ex. 9b 350 ppm 40.029.4 25.3 17.2

Example 10 Number of Post-Development Defects after DI Rinse vs. ProcessSolution Rinse

The number of post-development defects on a substrate was compared aftertreating the substrate with a rinse of DI water (comparative example 2)vs. a rinse containing the process solution of the present invention(example 10). The process solution contained 50 ppm of a2,5,8,11-tetramethyl-6-dodecyne-5,8-diol-derived surfactant and 170 ppmof the oligomer dispersant SMA® 1440 provided by Elf Alfochem. Thesubstrate was processed in the following manner: a photoresist-coatedsubstrate was exposed to a 365 nm light, heated to a temperature ofapproximately 110° C. for a time of about 1 minute and then developed toform a patterned photoresist with a dilute TMAH solution. The TMAHsolution was applied by dynamically dispensing a 0.21N TMAH solutiononto the substrate for a period of 100 seconds.

In comparative example 2, a rinse containing DI water started 15 secondsbefore the developer nozzle was turned off and continued for a period of7 minutes. The substrate was inspected for defects using the TereStar®KLA-Tencor defect inspection tool provided by KLA-Tencor Inc. of SanJose, Calif. and the defects were classified and counted. The results ofthe inspection are provided in Table V.

The substrate was processed in the same manner as in comparative example2 using the same developer and process conditions. However, after 100seconds of developing, a process solution comprising an acetylenic diolsurfactant (example 10) was used to rinse the patternedphotoresist-coated surface. The overlapping period with the developerwas the same as in comparative example 2. After a 120 second rinse withthe process solution, a DI water rinse was used for another 7 minutes.The substrate was inspected for defects using the TereStar® KLA-Tencordefect inspection tool and the defects were classified and counted. Theresults of the inspection are provided in Table VI.

As Table VI illustrates, the process solution of the present inventionwas able to completely remove the photoresist residues from thepatterned photoresist surface. By contrast, Table V shows that were manydefects resulting from residual photoresist and other sources afterrinsing with DI water. Therefore, rinsing the substrate with the processsolution of the present invention effectively eliminated the number ofpost-development defects and improved the process yield. TABLE VPost-Development Defects after DI Water Rinse Defect Types Small MediumLarge Extra large Total Pattern Defect 0 55 35 1 91 Pinholes/Dots 0 1482 0 150 Total 0 203 37 1 241

TABLE VI Post-Development Defects after Process solution Rinse DefectTypes Small Medium Large Extra large Total Pattern Defect 0 0 0 0 0Pinholes/Dots 0 0 0 0 0 Total 0 0 0 0 0

Example 11 Comparison of Equilibrium Surface Tension and Dynamic SurfaceTension of Process Solution vs. Solutions Containing Fluorosurfactant

Process solutions containing 0.1 weight percent of a surfactant derivedfrom 2,5,8,11-tetramethyl-6-dodecyne-5,8-dioland a fluorosurfactant,potassium perfluorooctane carboxylate provided by 3M of St. Louis, Mo.were prepared in order to compare the equilibrium surface tension (EST)and dynamic surface tension (DST). The EST for both solutions wasmeasured using the Wilhemy plate method on a Kruss BP3 bubble pressuretensiometer manufactured by Kruss, Inc. of Charlotte, N.C. The DST ofeach process solution was measured via the maximum bubble pressuremethod used in examples 1 through 5. The results of the EST and DSTtests are provided in Table VII.

Referring to Table VII, while the fluorosurfactant exhibits a lower ESTcompared to the process solution of the present invention, thesignificantly lower DST indicates that the fluorosurfactant exhibitspoor dynamic surface tension reduction ability. For applications thatrequire high surface creation rates such as dynamic rinse processes usedin semiconductor manufacturing, the process solution of the presentinvention would be more suitable than solutions containingfluorosurfactants due to its lower DST value. TABLE VII RinseComposition (0.1 wt %) EST (dyne/cm) DST (cm/cm) Example 11 25.8 28.4Fluorosurfactant 21.2 72.4

Examples 12 Through 18 Determination of the Adhesion Tension Value ofProcess Solutions of the Present Invention

Seven process solutions containing surfactants having the formulas Ithrough VIII were prepared by adding less than 1 weight percent of thesurfactant to deionized water under continuous stirring. Theconcentration of surfactant within each process solution is provided inTable VIII and is determined by the smallest adhesion tension valuecalculated at different concentrations for each surfactant. Example 12contained 3,5-dimethyl-1-hexyn-3-ol (Formula III). Example 13 contained2,6-dimethyl-4-heptanol provided by Aldrich (Formula IVa). Example 14contained N,N′-bis(1,3-dimethylbutyl)ethylenediamine (Formula V).Example 15 contained diisopentyl tartrate (Formula II). Example 16contained dodecyltrimethylammonium chloride (Formula IVa). Example 17contained 2,4,7,9-tetramethyl-4,7-decane diol (Formula V). Example 18contained 2,5,8,11-tetramethyl-6-dodecyne-5,8-diol-derived surfactant(Formula II). Examples 19, 20, and 21 each contained 1:3 adduct (0.05 wt% concentration), 1:5 adduct (0.012 wt % concentration), and 1:5 adduct(0.03 wt % concentration), respectively, of diethylenetriamine (x=2) andn-butyl glycidyl ether (Formula VIII).

The dynamic surface tension (DST) data for each process solution wascollected via the maximum bubble pressure method described in Langmuir1986, 2, pp. 428-432. The data was collected at bubble rates that rangefrom 0.1 bubbles/second (b/s) to 20 b/s using the Kruss BP3 bubblepressure tensiometer manufactured by Kruss, Inc. of Charlotte, N.C. Thesurface tension values at 0.1 bubbles/second for each process solutionare provided in Table VIII.

Silicon wafers provided by Wafernet Inc. of San Jose, Calif. were coatedwith 300 nm thick TOK 6063 193 nm photoresist coating provided by TokyoOhka Kogyo Co., Ltd. of Tokyo, Japan. The contact angle of the processsolution on the photoresist surface was measured on the G10/DSA10 Krussdrop shape analyzer provided by Kruss USA of Charlotte, N.C. using theSessile drop method. Table VIII provides the contact angle for eachprocess solution measured at a drop age of 10 seconds.

The adhesion tension values for each process solution was calculated bymultiplying the surface tension and the cosine of the contact angle. Theresults of this calculation are provided in Table VIII. As Table VIIIillustrates, all of the process solutions have an adhesion tension valuebelow 25. Examples 13, 14, 16, 19, 20, and 21 each had an adhesion valuebelow 20. This indicates that these process solutions may reduce thenumber of pattern collapse defects to a greater degree than a processsolution having one or more surfactants with a higher adhesion tensionvalue. TABLE VIII Adhesion Tension Values Examples 12 13 14 15 16 17 1819 20 21 Concentration 0.9 0.12 0.095 0.05 4 0.05 0.045 0.05 0.012 0.03(wt %) Surface 36.6 41.4 32.0 35.4 41.5 38.4 25.8 38.7 37.9 35.6 Tension(ST) (dynes/cm) Contact Angle 55.0 70.7 53.1 45.5 62.7 56.1 28.1 59 59.259.7 (θ) Adhesion 21.0 13.6 19.2 24.8 19.0 21.4 22.8 19.9 19.4 17.9Tension ValuePattern Collapse Reduction

Example 12, 14, and 17 process solutions were prepared by adding 0.9weight % of 3,5-dimethyl-1-hexyn-3-ol, 0.095 weight % ofN,N′-bis(1,3-dimethylbutyl)ethylenediamine, and 0.05 weight percent of2,4,7,9-tetramethyl-4,7-decane diol, respectively, to deionized waterunder continuous stirring. A substrate was processed in the followingmanner: a silicon wafer provided by Wafernet, Inc. and coated with ananti-reflective coating was coated with a TOK 6063 193 nm photoresistand exposed to a 193 nm light with a ASML PAS 5500/1100 scanner, heatedto a temperature of approximately 115° C. for a time of about 1 minute,and then developed to form a patterned photoresist with a dilute TMAHsolution. The TMAH developer solution was applied by dynamicallydispensing a 0.26N TMAH solution onto the substrate and allowed to setfor a period of 45 seconds. The process solution was then dynamicallydispensed onto the substrate surface while the wafer substrate slowlyspun at 500 rpm to distribute the solution on the substrate surface. Thedispense process lasted for a period of 15 seconds. Afterwards, thesubstrate was spun at 3,500 rpm to dry.

In a comparative example, a deionized water rinse solution was appliedthe substrate surface after the development of the patterned photoresistcoating with a TMAH developer solution under the same process conditionsas the Example 12, 14, and 17 process solutions.

Silicon wafers treated with a post-development rinse of the processsolution of the present invention and a deionized water post-developmentrinse were compared under scanning electron microscopy. FIGS. 1 a and 1b provide cross-sectional SEM images of 80 nm dense lines with 1:1 pitchusing a deionized water rinse and a rinse employing the Example 14process solution, respectively. Referring to FIG. 1 b, employing theprocess solution of the present invention as a post-development rinsesolution in addition to or in lieu of deionized water minimizes orreduces the incidence of pattern collapse and preserves line definition.

The critical dimensions (“CD”) of the features of each wafer weremeasured with a Hitachi CD-SEM tool on 37 sites per wafer, and patterncollapse was visually observed through the top-down SEM images. Thewafers were exposed under the same dose energy of 16.5 mJ/cm². Theresults of the visual observations are provided in Table IX.

As shown in Table IX, the process solutions of the present inventionreduced the collapsed sites by at least half while increasing the aspectratio from 3 to 3.3. Therefore, rinsing the substrate with the processsolution of the present invention rather than with deionized watereffectively reduced the pattern collapse when patterning high aspectratio features. TABLE IX Pattern Collapse Data % sites Rinse SolutionAspect Ratio with collapsing DI Water 3.0 97 Example 12 3.3 48 Example14 3.2 3 Example 17 3.1 6Reduction in Line Width Roughness

Exemplary process solutions 22 and 23 were prepared by adding 0.05weight % of N,N′-bis(1,3-dimethylbutyl)ethylenediamine (Formula Vsurfactant) and 0.05 weight % of 2,6-dimethyl-4-heptanol (Formula IIIsurfactant); and adding 0.1 weight % of 1:5 adduct of diethylenetriamine(x=2) and n-butyl glycidyl ether (Formula VIII surfactant),respectively, to deionized water under continuous stirring. A substratewas processed in the following manner: a silicon wafer provided byWafernet, Inc. and having an anti-reflective coating deposited thereuponwas coated with a TOK 6063 193 nm photoresist. The coated wafer wasexposed to a 193 nm light with a ASML PAS 5500/1100 scanner, heated to atemperature of approximately 115° C. for a time of about 1 minute, andthen developed to form a patterned photoresist with a dilute TMAHsolution. The TMAH developer solution was applied by dynamicallydispensing a 0.26N TMAH solution onto the substrate and allowed to setfor a period of 45 seconds. After 15 seconds of a DI water rinse, thesubstrate was spun at 3,500 rpm to dry. The wafer was then cleaved intosmaller pieces, immersed into either deionized water, Example 22 processsolution, or the Example 23 process solution for 15 seconds and thendried. Cross-sectional SEM pictures showing 100 nm 1:1 dense lines weretaken before and after the treatment process.

FIGS. 2 a through 2 c provide cross-sectional SEM images of the wafers.FIG. 2 a shows that the patterned resist features of substrates treatedwith DI water alone exhibited rough standing waves. However, upontreatment with process solutions 22 or 23, such as the substrates shownin FIGS. 2 b and 2 c, respectively, the patterned resist features aremuch smoother and the standing wave is eliminated.

Examples 24 and 25

Exemplary process solutions 24 and 25 were prepared by adding 0.12weight % of N,N′bis(1,3-dimethylbutyl)ethylenediamine (Formula Vsurfactant) and 5 weight % of the non-aqueous solvent ethanol andmethanol, respectively to deionized water under continuous stirring. Anadditional process solution Example 14 was prepared as previouslydescribed by adding N,N′bis(1,3-dimethylbutyl)ethylenediamine (Formula Vsurfactant) to deionized water alone.

A substrate was processed in the following manner: a silicon oxynitridewafer was coated with a 193 nm photoresist. The coated wafer was exposedto a 193 nm light with a ASML PAS 5500/950 scanner, heated to atemperature of approximately 115° C. for a time of about 1 minute, andthen developed to form a patterned photoresist with a dilute TMAH. TheTMAH developer solution was applied by dynamically dispensing a 0.26NTMAH solution onto the substrate and allowed to set for a period of 45seconds. The process solution was then dynamically dispensed onto thesubstrate surface while the wafer substrate spun slowly at 500 rpm todistribute the solution on the substrate surface. The wafer was thenstill and puddle underneath the process solution for 5 seconds.Afterwards, the substrate was spun at 3,500 rpm to dry.

The top-down SEM was used to collect the LWR measures at 100 nmlines/space at 1:1 pitch and the results for each process solution areprovided in Table X. Table X also provides the maximum energy doseapplied to the wafer without causing the collapse of patterned resistfeatures and the corresponding minimum CD as well as the maximum aspectratio. TABLE X Mean CD and LWR results Maximum Energy Minimum CD MaximumLWR Process Solution (mJ/cm2) (nm) Aspect Ratio (3σ, nm) Ex. 14 23.25103.6 2.90 5.5 Ex. 24 25.5 92.5 3.24 5.4 Ex. 25 24.75 94.3 3.18 4.8

1. A method for reducing the number of defects during the manufacture ofsemiconductor devices, the method comprising: providing a substratecomprising a photoresist coating; exposing the substrate to a radiationsource to form a pattern on the photoresist coating; applying adeveloper solution to the substrate to form a patterned photoresistcoating; optionally rinsing the substrate with deionized water; andcontacting the substrate with a process solution comprising at least oneaqueous solvent, at least one non-aqueous solvent that is miscible in anaqueous solvent, and about 10 ppm to about 10,000 ppm of at least onesurfactant having the formula (I), (II), (III), (IVa), (IVb), (V), (VI),(VII), (VIII), (IXa), (IXb), (IXc), (Xa), (Xb), (Xc), or (Xd):

wherein R, R₁, R₄, and R₁₂ are each independently a straight, abranched, or a cyclic alkyl group having from 3 to 25 carbon atoms; R₂and R₃ are each independently a hydrogen atom or an alkyl group havingfrom 1 to 5 carbon atoms; R₅ is a straight, a branched, or a cyclicalkyl group having from 1 to 10 carbon atoms; R₆ is a straight, abranched, or a cyclic alkyl group having from 4 to 16 carbon atoms; R₇,R₈, and R₉ are each independently a straight, a branched, or a cyclicalkyl group having from 1 to 6 carbon atoms; R₁₀ is independently H or agroup represented by the formula

R₁₁ is a straight, a branched, or a cyclic alkyl group having from 4 to22 carbon atoms; W is a hydrogen atom or an alkynyl group; X and Y areeach independently a hydrogen atom or a hydroxyl group; Z is a halideatom, a hydroxyl group, an acetate group, or a carboxylate group; i, m,n, p, and q are each independently a number that ranges from 0 to 20; rand s are each independently 2 or 3; t is a number that ranges from 0 to2; j is a number that ranges from 1 to 5; and x is a number that rangesfrom 1 to
 6. 2. The method of claim 1 wherein the contacting stepcomprises a dynamic rinse.
 3. The method of claim 1 wherein thecontacting step comprises a static rinse.
 4. The method of claim 1wherein the surface of the substrate in the contacting step is wet withthe developer solution.
 5. The method of claim 1 wherein the surface ofthe substrate in the contacting step is wet with the deionized waterrinse.
 6. The method of claim 1 wherein the process stream is formed byinjecting 10 to 10,000 ppm of the at least one surfactant into thesolvent.
 7. The method of claim 1 wherein the process stream is formedby applying 10 to 10,000 ppm of the at least one surfactant onto thesurface of the substrate and applying the solvent to the substratesurface.
 8. The method of claim 1 wherein the process stream is formedby passing the solvent through a cartridge comprising the at least onesurfactant.
 9. The method of claim 1 wherein a time of the contactingstep ranges from 1 to 200 seconds.
 10. The method of claim 9 wherein thetime of the contacting step ranges from 1 to 150 seconds.
 11. The methodof claim 10 wherein the time of the contacting step ranges from 1 to 40seconds.
 12. The method of claim 10 wherein an at least one temperatureof the contacting step ranges from 10 to 100° C.
 13. A method foravoiding a collapse of a developed pattern on the surface of a pluralityof substrates, the method comprising: providing a first substratecomprising a photoresist pattern developed upon the surface; preparing aprocess solution comprising from 10 ppm to about 10,000 of at least onesurfactant having the formula (I), (II), (III), (IVa), (IVb), (V), (VI),(VII), (VIII), (IXa), (IXb), (IXc), (Xa), (Xb), (Xc), or (Xd):

wherein R, R₁, R₄, and R₁₂ are each independently a straight, abranched, or a cyclic alkyl group having from 3 to 25 carbon atoms; R₂and R₃ are each independently a hydrogen atom or a straight, a branched,or a cyclic alkyl group having from 1 to 5 carbon atoms; R₅ is astraight or a branched alkyl group having from 1 to 10 carbon atoms; R₆is a straight or a branched alkyl group having from 4 to 16 carbonatoms; R₇, R₈, and R₉ are each independently a straight or a branchedalkyl group having from 1 to 6 carbon atoms; R₁₀ is independently a Hatom or a group represented by the formula

R₁₁ is a straight, branched, or cyclic alkyl group having from 4 to 22carbon atoms; W is a hydrogen atom or an alkynyl group; X and Y are eachindependently a hydrogen atom or a hydroxyl group; Z is a halide atom, ahydroxyl group, an acetate group, or a carboxylate group; i, m, n, p,and q are each independently a number that ranges from 0 to 20; r and sare each independently 2 or 3; t is a number that ranges from 0 to 2; jis a number that ranges from 1 to 5; and x is a number that ranges from1 to 6; contacting the first substrate with the process solution;determining a surface tension and a contact angle of the processsolution on the first substrate; multiplying the surface tension by thecosine of the contact angle to provide the adhesion tension value of theprocess solution; providing the plurality of substrates wherein eachsubstrate within the plurality comprises a photoresist pattern developedupon the surface; and contacting the plurality of substrates with theprocess solution if the adhesion tension value of the process solutionis 30 or below.
 14. The process of claim 13 wherein the preparing, thefirst contacting, the determining, and the multiplying steps arerepeated until the adhesion tension value is 30 or below.
 15. Theprocess of claim 13 wherein the surface of the plurality of substratesin the second contacting step is wet with a deionized water rinse. 16.The process of claim 13 wherein the surface of the plurality ofsubstrates is wet with a developer solution.
 17. A method of reducingpattern collapse defects on the surface of a patterned and developedsubstrate comprising: contacting the substrate with a process solutioncomprising an aqueous solvent, a non-aqueous solvent, and at least onesurfactant having the formula (I), (II), (III), (IVa), (IVb), (V), (VI),(VII), (VIII), (IXa), (IXb), (IXc), (Xa), (Xb), (Xc), or (Xd):

wherein R, R₁, R₄, and R₁₂ are each independently a straight, abranched, or a cyclic alkyl group having from 3 to 25 carbon atoms; R₂and R₃ are each independently a hydrogen atom or a straight, a branched,or a cyclic alkyl group having from 1 to 5 carbon atoms; R₅ is astraight, a branched, or a cyclic alkyl group having from 1 to 10 carbonatoms; R₆ is a straight, a branched, or a cyclic alkyl group having from4 to 16 carbon atoms; R₇, R₈, and R₉ are each independently a straight,a branched, or a cyclic alkyl group having from 1 to 6 carbon atoms; R₁₀is a hydrogen atom or a group represented by the formula

R₁₁ is a straight, a branched, or a cyclic alkyl group having from 4 to22 carbon atoms; W is a hydrogen atom or an alkynyl group; X and Y areeach independently a hydrogen atom or a hydroxyl group; Z is a halideatom, a hydroxyl group, an acetate group, or a carboxylate group; i, m,and n are each independently a number that ranges from 0 to 20; r and sare each independently 2 or 3; t is a number that ranges from 0 to 2; jis a number that ranges from 1 to 5; and x is a number that ranges from1 to
 6. 18. A method of reducing line width roughness defects on thesurface of a patterned and developed substrate comprising: contactingthe substrate with a process solution comprising an aqueous solvent, anon-aqueous solvent, and at least one surfactant having the formula (I),(II), (III), (IVa), (IVb), (V), (VI), (VII), (VIII), (IXa), (IXb),(IXc), (Xa), (Xb), (Xc), or (Xd):

wherein R, R₁, R₄, and R₁₂ are each independently a straight, abranched, or a cyclic alkyl group having from 3 to 25 carbon atoms; R₂and R₃ are each independently a hydrogen atom or a straight, a branched,or a cyclic alkyl group having from 1 to 5 carbon atoms; R₅ is astraight, a branched, or a cyclic alkyl group having from 1 to 10 carbonatoms; R₆ is a straight, a branched, or a cyclic alkyl group having from4 to 16 carbon atoms; R₇, R₈, and R₉ are each independently a straight,a branched, or a cyclic alkyl group having from 1 to 6 carbon atoms; R₁₀is a hydrogen atom or a group represented by the formula

R₁₁ is a straight, a branched, or a cyclic alkyl group having from 4 to22 carbon atoms; W is a hydrogen atom or an alkynyl group; X and Y areeach independently a hydrogen atom or a hydroxyl group; Z is a halideatom, a hydroxyl group, an acetate group, or a carboxylate group; i, m,and n are each independently a number that ranges from 0 to 20; r and sare each independently 2 or 3; t is a number that ranges from 0 to 2; jis a number that ranges from 1 to 5; and x is a number that ranges from1 to 6.